Laser shock peening (LSP) with different cycles was performed on the Ti-based bulk metallic glasses (BMGs). The internal residual stress of the LSPed specimens was measured by high-energy X-ray diffraction (HEXRD) and the residual stress on the shocked surface was measured by scanning electron microscope/focused ion beam (SEM/FIB) instrument. The internal residual stress in the LSP impact direction (about -170 MPa) is much lower than that perpendicular to the impact direction (about -350 MPa), exhibiting anisotropy. The depth of the compressive stress zone increases from 400 μm to 500 μm with increasing LSP cycles. The highest residual stress on the shocked surface is about -750 MPa. LSP caused the free volume to increase and the maximum increase appeared after the first LSP process. Compared with the hardness (567±7 HV) of the as-cast BMG, the hardness (590±9 HV) on the shocked surface shows a hardening effect due to the hardening mechanism of compressive residual © 2016. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/ 2 stress; and the hardness (420±9 HV) on the longitudinal section shows a softening effect due to the softening mechanism of free volume.